Highly active and selective Cu-ZnO based catalyst for methanol and dimethyl ether synthesis via CO2 hydrogenation

Ren, Shoujie; Shoemaker, Weston R.; Wang, Xiaofeng; Shang, Zeyu; Klinghoffer, Naomi; Li, Shiguang; Yu, Miao; He, Xiaoqing; White, Tommi; Liu, Xinhua

doi:10.1016/j.fuel.2018.11.105

Cited by 97 publications

(45 citation statements)

References 53 publications

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“…As for the samples prepared using the hydrotalcite method, it can be observed that the catalyst composition affected their surface characteristics. Although the values of MSA resulted slightly lower (17.2-24.6 m 2 /g) than that on the commercial catalyst (32.4 m 2 /g), leading to a minor metal dispersion (11.6%-16.7%), the obtainment of just larger copper particles (6.2-9.0 nm) could result beneficial for catalytic activity, due not only to a better resistance to the metal sintering during reaction, but also to a more favorable interaction between the metal and the carrier oxide(s) [22,23].…”

Section: Physico-chemical Propertiesmentioning

confidence: 99%

Tailoring of Hydrotalcite-Derived Cu-Based Catalysts for CO2 Hydrogenation to Methanol

et al. 2019

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Ternary Cu x Zn y Al z catalysts were prepared using the hydrotalcite (HT) method. The influence of the atomic x:y:z ratio on the physico-chemical and catalytic properties under CO 2 hydrogenation conditions was probed. The characterization data of the investigated catalysts were obtained by XRF, XRD, BET, TPR, CO 2 -TPD, N 2 O chemisorption, SEM, and TEM techniques. In the "dried" catalyst, the typical structure of a hydrotalcite phase was observed. Although the calcination and subsequent reduction treatments determined a clear loss of the hydrotalcite structure, the pristine phase addressed the achievement of peculiar physico-chemical properties, also affecting the catalytic activity. Textural and surface effects induced by the zinc concentration conferred a very interesting catalyst performance, with a methanol space time yield (STY) higher than that of commercial systems operated under the same experimental conditions. The peculiar behavior of the hydrotalcite-like samples was related to a high dispersion of the active phase, with metallic copper sites homogeneously distributed among the oxide species, thereby ensuring a suitable activation of H 2 and CO 2 reactants for a superior methanol production.Catalysts 2019, 9, 1058 2 of 15 hydroxycarbonate precursors [8][9][10]. On this account, studies on binary Cu x Zn y preparations enabled a deep understanding of the more complex ternary (Cu/Zn/Al) systems. Therefore, in binary preparations, typical crystalline phases range from Cu-rich to Zn-rich compositions, including malachite Cu 2 (OH) 2 CO 3 , zincian malachite (Cu x Zn y ) 2 (OH) 2 CO 3 , aurichalcite (Cu x Zn y ) 5 -(OH) 6 (CO 3 ) 2 , and hydrozincite Zn 5 (OH) 6 (CO 3 ) 2 . In particular, zincian malachite is currently considered to be the optimum precursor for the methanol synthesis catalyst, which facilitates formation of a highly porous meso-structure [11]. Considering that the maximum amount of Zn which can be substituted into the malachite lattice is 27 at.%, the optimum Cu:Zn molar ratio is close to 2:1 [12]. Higher Zn contents are desirable to facilitate further dilution of the Cu component, thereby enhancing metal dispersion, although this can result in a lower crystallinity of the zincian malachite phase. The final thermal decomposition of the hydroxycarbonates leads the formation of an intimate mixture of oxides, while an in situ reduction step is required to obtain the active catalyst.Recent approaches to synthesize methanol via catalytic hydrogenation of CO 2 , as the key for an anthropogenic chemical carbon cycle along with the need to reduce the economic impact of the conventional high-pressure synthesis of methanol via syngas, now address the research efforts toward novel preparation methods suitable for obtaining catalytic systems characterized by high copper dispersion and surface basicity to enhance CO 2 adsorption [13][14][15], as the competitive reaction pathway of reverse water gas shift (RWGS) leads to a loss of methanol production [16,17]. Therefore, appropriate adsorption amount a...

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Section: Physico-chemical Propertiesmentioning

confidence: 99%

Tailoring of Hydrotalcite-Derived Cu-Based Catalysts for CO2 Hydrogenation to Methanol

et al. 2019

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“…Furthermore, the presence of CO 2 increased the oxidation rate of the metal particles (e.g., copper), and a higher amount of hydrogen or more stable catalysts were then requested [ 53 ].…”

Section: Resultsmentioning

confidence: 99%

Process Simulation and Environmental Aspects of Dimethyl Ether Production from Digestate-Derived Syngas

Giuliano

Catizzone

Freda

2021

IJERPH

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The production of dimethyl ether from renewables or waste is a promising strategy to push towards a sustainable energy transition of alternative eco-friendly diesel fuel. In this work, we simulate the synthesis of dimethyl ether from a syngas (a mixture of CO, CO2 and H2) produced from gasification of digestate. In particular, a thermodynamic analysis was performed to individuate the best process conditions and syngas conditioning processes to maximize yield to dimethyl etehr (DME). Process simulation was carried out by ChemCAD software, and it was particularly focused on the effect of process conditions of both water gas shift and CO2 absorption by Selexol® on the syngas composition, with a direct influence on DME productivity. The final best flowsheet and the best process conditions were evaluated in terms of CO2 equivalent emissions. Results show direct DME synthesis global yield was higher without the WGS section and with a carbon capture equal to 85%. The final environmental impact was found equal to −113 kgCO2/GJ, demonstrating that DME synthesis from digestate may be considered as a suitable strategy for carbon dioxide recycling.

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“…This deactivation can be caused by the competing adsorption of water, dimers, trimers, or even larger alcohol-water clusters, but also the (reversible) formation of (surface) boehmite was shown. 27 Despite the large attention for more active low-temperature methanol dehydration catalysts, 4,6,59,69,71,73,74,[76][77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95] γ-Al 2 O 3 remains the catalyst of choice for industrial DME production, due to its low cost, high surface area, good thermal and mechanical stability, and high selectivity to DME because its relatively weak Lewis acid sites do not promote side reactions. 4,70,96,97 In contrast to direct DME synthesis, SEDMES offers two specific advantages for the (γ-Al 2 O 3 ) catalyst: the system is operated at low steam pressures and is periodically regenerated due to its adsorptive nature.…”

Section: Steam Adsorbentmentioning

confidence: 99%

Sorption enhanced dimethyl ether synthesis under industrially relevant conditions: experimental validation of pressure swing regeneration

et al. 2021

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Highly active and selective Cu-ZnO based catalyst for methanol and dimethyl ether synthesis via CO2 hydrogenation

Cited by 97 publications

References 53 publications

Tailoring of Hydrotalcite-Derived Cu-Based Catalysts for CO2 Hydrogenation to Methanol

Tailoring of Hydrotalcite-Derived Cu-Based Catalysts for CO2 Hydrogenation to Methanol

Process Simulation and Environmental Aspects of Dimethyl Ether Production from Digestate-Derived Syngas

Sorption enhanced dimethyl ether synthesis under industrially relevant conditions: experimental validation of pressure swing regeneration

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